Lignin Production and

Conversion Technologies

Arvind Lali
Aruna N, Prathamesh Wadekar, Mallikarjun Patil,
Parmeshawar Patil, Nikhil Asodekar; Suveera Bellary
DBT-ICT Centre for Energy Biosciences
Institute of Chemical Technology (formerly UDCT)
Mumbai, INDIA 400019
am.lali@ictmumbai.edu.in
Mumbai

INDIA
Institute of Chemical Technology
(formerly UDCT)
at Matunga (Central Suburb)
DBT-ICT Centre for Energy Biosciences
Matunga, Mumbai
DBT-ICT Centre of Energy Biosciences
(Sanctioned Dec 2007; Functional May 2009)

- India’s first National Bioenergy Research Centre

- Set up at a cumulative cost of about 15 million USD

- Multidisciplinary State-of-the-Art facility with emphasis on

developing cutting-edge science and translation to commercially
viable technologies

- Networked with Institutions & Industry in India and abroad

>50 PhD scholars; >10 Senior Research Scientists

in different disciplines of modern biological sciences and chemical
engineering/technology
 Centre’s Overall RDD&D Objectives
Development, Demonstration and Transfer
Cost effective and Sustainable Biomass to Biofuel technologies

Building capacity in the field of Industrial Biotechnology

Capacity & Technology Technology

HR Generation Development Deployment
Infra Building
 Sustainable Platform Technologies

Waste

Utilizable Carbon

Smart Chemical/Biotech
Conversion Technologies

Food/Feed/Energy/Materials & Chemicals

400
400
 Biomass to Renewables: Technology Options

Biomass
Combustion Digestion
Power
Gasification Biogas/BioCNG
Fast Pyrolysis/
SCWG

Syn-Gas Bio-Oil Fermentable

Sugars
Catalysis
Fermentation/
Chemical Catalysis FT Synthesis
Hydrocarbons
Hydrocarbons & BioFuels
Platform Cracking
Chemicals
Chemicals
Platform Chemicals
Gasoline, Diesel Hydrocarbons
 Biomass to Renewables: Technology Options

Biomass
Combustion Digestion
Power
Gasification Biogas/BioCNG
Fast Pyrolysis/
SCWG

Syn-Gas Bio-Oil Fermentable

Fermentation/
Preferred Technology
Catalysis
Sugars
Chemical Catalysis FT Synthesis Platform
Hydrocarbons
Hydrocarbons & BioFuels
Platform Cracking
Chemicals
Chemicals
Platform Chemicals
Gasoline, Diesel Hydrocarbons
TYPICAL PROCESS OUTLINE Lignocellulosic Biomass

STEP 1 Pre-Treatment Step

STEP 2 Saccharification LIGNIN

STEP 3 Fermentation

STEP 4 Separation/Purification
Biofuel
 Typical 2G-Bioethanol and Pulping Process

Enzyme
Fermentation
Biomass Fractionation hydrolysis of
to ethanol
carbohydrates

Lignin to
Boiler Does it deserve more than
just burning

Kraft and
Paper and
Biomass Lignosulfonate
pulp
Process
 Routes to Lignin Utilization

Lignin

Used in As-Derived form for Break-down

integrating into partially or fully
More complex Polymeric structures
e.g. formulating resins; as polymeric filler
Reconstruct
Products through
Biological or Chemical
technologies
 Routes to Lignin Utilization
Way to go for
Lignin Better value

Used in As-Derived form for Break-down

integrating into partially or fully
More complex Polymeric structures
e.g. formulating resins; as polymeric filler
Reconstruct
Attempted with Products through
Limited successes Biological or Chemical
technologies
Next Generation Lignin Technologies
Lignin Isolation & Deconstruction technologies
Lignin  Depolymerization  Polishing

Conversion technologies
Lignin monomers  Conversion  Products

Biological Methods and Chemical Methods

 Part 1
Lignin Isolation and
Deconstruction Technologies
Chemical and Biological
Lignin : A Polymeric structure closely linked with
Itself, Cellulose and Hemicellulose
Lignin-Carbohydrate bonding
Lignin Intra-Bonding
Linkage type % of total linkage
Softwood Hardwood
β-O-4 50 60
4-O-5 4 7
β-5 9-12 6
5-5 10-11 5
β-1 7 7
β-β 2 3

Wood type Coniferyl alcohol Sinapyl alcohol p-coumaryl

alcohol

Softwood 75% 20% 5%

Hardwood 50% 40% 10%

20
2G Biofuels: Lignin Production Technologies
Process Typical Conditions Lignin Recovery Method
Pulping based Lignin Production Technologies
Lignin Properties
Dilute acid MW 5000 10000 Da
Sulphur content – 0 – 1.0 % (dilute Sulphuric acid process)
Condensed structure
Alkali MW 2700 -6000 Da
Sulphur free process
Accounts for nearly 5% of the total pulp production
Steam explosion MW 2500-11000 Da (lignin obtained from softwood)
(softwood) No Sulphur content
Condensed structure, lower methoxy but higher hydroxyl group
AFEX MW 5000Da
No Sulphur content
The method cannot be used for >25% lignin content biomass
Klason MW 8000 – 9000 Da
Sulphur content – 4-5%
Condensed structure
Organosolve MW 3300 Da (Lignin obtained from hardwood)
(Alcell process) Sulphur free and less condensed structure
Kraft Process MW 6000-10000Da
1.5–3 wt% Sulphur content
Dominant pulping process in world
Lignosulfonate MW 12000Da-65000 Da
4–8% Sulphur content (so higher mol wt)
10% of pulp is produced by this method
Comparison of different Isolated
Polymeric Lignins
Isolated Lignin: Technologies for Deconstruction
to its Monomeric Components

Chemical Methods

Biological Methods
 Chemical Depolymerization and
Conversion of Lignin
OH HO O OH

O O
Hydrothermal
Liquefaction Catalysis 2
Phenol, Phenolic derivatives and
Catalysis 1 oligomeric aromatic phenols
Lignin +
Char Gases

Kraft OH

Lignosulfonate Polymers
Dilute acid Pyrolysis and
C5-C9
Catalysis 2
Alkali Hydrocatapyrolysis Fuel
Aromatic and aliphatic hydrocarbons,
Steam Catalysis 1
alkoxy phenol and darivative
explosion + Bulk and Fine
Char Gases
AFEX Chemical s
Organosolve
Char Catalysis/
Klason + Fermentation
Gasification
Dil. Ammonia Syngas
CO,H2, CO2,CH4
 Chemical Depolymerization and
Conversion of Lignin
OH HO O OH

O O
Hydrothermal
Liquefaction Catalysis 2
Phenol, Phenolic derivatives and
Catalysis 1 oligomeric aromatic phenols
Lignin +
Char Gases

Kraft Technology Bottlenecks OH

Low conversions in Catalysis Step 1

Lignosulfonate Polymers
Dilute acid C5-C9

Alkali ComplexHydrocatapyrolysis
catalysis required in Step 2Catalysis 2
Pyrolysis and
Fuel
Aromatic and aliphatic hydrocarbons,
Steam Catalysis 1
alkoxy phenol and darivative
explosion + Bulk and Fine
Char Gases
AFEX Chemical s
Organosolve
Char Catalysis/
Klason + Fermentation
Gasification
Dil. Ammonia Syngas
CO,H2, CO2,CH4
Bioconversion of Lignin:
Past, Present and Future

1990 – 2015
Bacterial lignin degradation studied in
Nocardia, Pseudomonas and
Actinomycetes
Bacterial lignin degraders fall into
three categories actinomycetes, α-
1950 –1999 proteobacteria, γ-proteobacteria
Degradation studied in Sphingomonas paucimobilis SYK-6
Trametes extensively studied for catabolism of
Phanerochaete lignin compounds
chrysosporium used as Pseudomonas putida,
1939 model organism Rhodococcus species, Bacillus
Lignin degradation All peroxidases discovered species, Cupriviadus necator
studied in compost Laccase mediator discovered,
being targeted for genetic
environment molecular biology of fungal manipulation for
enzymes studied. biotransformation of lignin to
chemicals and fuels

Annele Hatakka in Bugg et al. Natural Products Reports, RSC Publishing, 2011, 1871-1960
Microbial Depolymerization of lignin

Microbial Lignin Depolymerization

Enzyme Concoctions

Auxiliary
Laccases Peroxidases
Enzymes

Depolymerized
Lignin components
 Microbial Depolymerization of lignin

Microbial Lignin Depolymerization

Enzyme Concoctions
Technology Bottlenecks
 Re-polymerization of lignin a major issue
Auxiliary
Laccases Peroxidases
pH and temperature critical factors Enzymes
Slow processes
Genetic manipulation of fungus tedious
Isolated enzymes very expensive (if available)
Depolymerized
Lignin components
 Part 2
Lignin Conversion Technologies
Chemical and Biological
 Chemical Conversions
of Lignin precursor chemicals obtained from
thermo chemical treatment to lignin

Catalysis Catalysis

PF Resins BTX, Syngas,

Polyester Gasoline range Fermentation
hydrocarbon s to Products
 Biological Conversion of Lignin
Designed microbial system to convert lignin derived
aliphatic and aromatics into Value added products

Lignin Lignin degrading

microbes Value added chemicals

Advantages
Not energy intensive
Eco-friendly
Selectivity and specificity of end products
 Future of Lignin Bioconversion Technologies

D Salavuchua et al.
Green Chemistry, RSC Publishing, 2015
 Development of Lignin Technologies at
DBT-ICT Centre for Energy Biosciences
Mumbai, India
 Base Catalyzed Biomass Pretreatment
.vs.
Acid/Hydrothermal Pretreatment

BASE
- Milder
- Ester hydrolysis
- Limited glycosidic hydrolysis
- Progressive steps
- delignification
- hemicellulose leaching
- No furanic formation
- Simple stainless Steel OK
- Higher concentrations required
- Recovery essential
ACID/HYDRO
- Severe conditions
- Ester & Ether Hydrolysis
- Considerable glycosidic hydrolysis
- Simultaneous steps
- Fractionation not performed
- Furanics formation
- Complex MOC
- Low concentrations
- Recovery not done
 Base Catalyzed Biomass Pretreatment
.vs.
Acid/Hydrothermal Pretreatment

BASE ACID/HYDRO
- Milder - Severe conditions
- Ester hydrolysis - Ester & Ether Hydrolysis
- Limited glycosidic hydrolysis -- Considerable glycosidic
Use of MF/UF/NF for hydrolysis
- Progressive steps - separation
Simultaneous
andsteps
recovery
- delignification
of -base
Fractionation not performed
- hemicellulose leaching
- No furanic formation -- Distillation if
Furanics formation
- Simple stainless Steel OK - aqueous
Complex ammonia
MOC used
- Higher concentrations required - Low concentrations
- Recovery essential - Recovery not done
Technology components tested at

A. Laboratory scale (ICT)

B. Preparatory scale (ICT)
C. Plant scale (IGL)

10 ton Biomass/day Pilot Plant

at
India Glycols Limited, Kashipur
Phase 1: Functional from February 2012
Phase 2: To begin production in Oct 2014
 Characterization of Lignin obtained from
alkali and acid pretreated Rice Straw
Lignin Types

NaOH Lignina NH3 Ligninb Acid Ligninc (Klason)

Compositional Molecular weight Thermal Structural

Functional group
analysis distribution behavior studies
analysis

Elemental FT-IR GPC TGA NMR

analysis, sugar
and ash Pretreatment process
analysis a- 10% NaOH, 130°C, 30min
b-12.5 to 25% NH3, 130°C to 150°C , 30min
c- 72% H2SO4, 30 °C, 60min
 Derived Lignin Analysis
Compositional Analysis Elemental Analysis
Samples Cellulose Hemicellulose Ash Purity Samples C H O N S
(%) as xylose (%) (%) (%)

NaOH 52.88 6.18 39.08 0.59 0.07

NaOH 6.08 26.14 2.18 65.60 lignin
lignin

NH3 2.88 2.53 7.74 86.85 NH3 lignin 56.51 5.18 27.02 4.71 0.71
lignin

Acid 13.50 1.21 4.30 80.99 Acid 49.50 4.53 32.69 0.56 4.51
(Klason) (Klason)
lignin lignin

Carbohydrate content was found to be higher in NaOH lignin as NaOH being stronger base, co-
extracts hemicellulose with lignin.

Higher ash content in NH3 lignin was mainly due to the insolubility of ammonium silicate in water

Reactivity of ammonia and sulphuric acid was confirmed from higher nitrogen and sulphur content in
NH3 and acid lignin.
 TGA analysis
0.9

0.8

0.7

Acid lignin
0.6
NaOH lignin Decomposition temperature
0.5 NH3 lignin Ammonia lignin < NaOH lignin < Acid lignin
0.4
Condensation
0.3 3520C Ammonia lignin < NaOH lignin < Acid lignin
0.2 3410C
4100C
0.1

0
0 100 200 300 400 500 600 700 800 900
Temperature (deg C)

Decomposition temperature of acid lignin was found to be higher than alkali lignins,
confirming undesirable condensation in acid pretreatment
 DBT-ICT Lignin Technologies

Dilute ammonia
c Lignin

Catalytic Depolymerization
c

Mining for Microbes with best

c
utilization and growth profiles

Metabolic Pathway Engineering

and Fermentation
c technology for
Value Adds
DBT-ICT Centre for Energy Biosciences, India
State-of-the-Art Facility with >100 scientists
Collaborations with Australian, UK and German Groups
Working with major companies in India and World
Setting up 5 biorefinery demo-plants to go
on-stream in 2016
Lignin specific collaborations most welcome

Thank you